Tricyanoborates

ABSTRACT

The present invention relates to novel tricyanoborates of the general formula Cat n+ [B(CN) 3 (XR 1 )]— n , wherein R 1  is C 1-6  alkyl, C 2-6  alkenyl, C 6-10  aryl or benzyl; X is oxygen or sulfur; and Cat n+  is a cation with n being 1 or 2, which is selected from the group consisting of an inorganic cation and an organic cation; and also their preparation and use.

This application is a US national phase of International Application No. PCT/EP2010/000426 filed on Jan. 26, 2010, which claims the benefit of European patent application 09001388.9, filed Feb. 2, 2009 and U.S. patent application Ser. No. 61/151,224, filed Feb. 10, 2009, the disclosures of which are incorporated herein by reference in their entirety.

The present invention relates to novel tricyanoborates, their use and processes for preparing them.

The term “ionic liquids” is usually used to refer to salts which are liquid at temperatures below 100° C., in particular at room temperature. Such liquid salts typically comprise organic cations and organic or inorganic anions.

The organic cations of ionic liquids are usually quaternary ammonium or phosphonium ions or cations of aromatic, usually nitrogen-containing bases which may be substituted by alkyl groups, halogen atoms or cyano groups and may contain further heteroatoms such as phosphorus, sulfur or oxygen. Examples of customary organic cations are imidazolium, oxazolium, pyrazinium, pyrazolium, pyridazinium, pyrrolidinium, pyridinium, thiazolium and triazolium cations.

Typical anions in ionic liquids are AlCl₄ ⁻, AsF₆ ⁻, BF₄ ⁻, Br⁻, CF₃SO₃ ⁻, (CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻, Cl⁻, CN⁻, SCN⁻, FeCl₃ ⁻, NO₃ ⁻, PF₆ ⁻, pyruvate, acetate, oxalate or the tricyanomethane anion described in EP-A-1 634 867. In addition, WO 2004/072089 and WO 2007/093961 disclose cyanoborate anions of the general formula [BF_(n)(CN)_(4-n)]⁻, wherein n is 0, 1, 2 or 3.

Ionic liquids have a series of interesting properties: Usually, they are thermally stable, relatively non-flammable and have a very low vapour pressure. In addition, they have very good solvent properties for numerous organic and inorganic substances. Owing to their ionic structure, ionic liquids also have interesting electrochemical properties, for example electrical conductivity which is often accompanied by a high electrochemical stability. Therefore, there is a fundamental need for new ionic liquids having a variety of properties which open up additional opportunities for their use.

It is an object of the present invention to provide novel stable compounds which can be used as ionic liquids or as precursors of ionic liquids, and also a process for preparing them. These compounds should be able to be disposed of in an environmentally friendly manner after use.

This object is achieved by the tricyanoborates according to claim 1, by their use according to claim 12 and by the processes for their preparation according to claims 13 and 14. Further preferred embodiments are the subject-matter of dependent claims.

The present invention relates to novel tricyanoborates of the general formula

wherein R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl, X is oxygen or sulfur, and Cat^(n+) is a cation with n being 1 or 2, which is selected from the group consisting of an inorganic cation M^(n+) and an organic cation Q^(n+) with n being 1 or 2.

Here and in the following, the expression “C_(1-n) alkyl” refers to any linear or branched alkyl group which contains from 1 to n carbon atoms. For example, the expression “C₁₋₆ alkyl” encompasses groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethyl-propyl), hexyl and isohexyl (4-methylpentyl).

Here and in the following, the expression “C_(2-n) alkenyl” refers to a carbon chain which is made up of from 2 to n carbon atoms and contains at least one double bond, with the carbon atoms being saturated by hydrogen atoms and the carbon chain being able to be branched. For example, the expression “C₂₋₄ alkenyl” encompasses groups such as ethenyl, 1-methylethenyl, prop-1-enyl, prop-2-enyl, 2-methylprop-2-enyl and buta-1,3-dienyl.

Here and in the following, the expression “C₆₋₁₀ aryl” refers to an aryl group which has from 6 to 10 carbon atoms and may be substituted by one or more C₁₋₄ alkyl or C₁₋₄ alkoxy groups. For example, “C₆₋₁₀ aryl” encompasses phenyl, benzyl, methylphenyl, methoxyphenyl, dimethylphenyl, ethylmethylphenyl, diethylphenyl and naphthyl.

Tricyanoborates of formula I, wherein X is oxygen, are preferred.

Tricyanoborates of formula I, wherein R¹ is C₁₋₆ alkyl, preferably methyl, ethyl or propyl, and more preferably methyl, are also preferred.

In a further preferred embodiment, the cation Cat^(n+) is an inorganic cation M^(n+) with n being 1 or 2, which is selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.

In an also preferred embodiment, the cation Cat^(n+) is an organic cation Q^(n+) with n being 1 or 2, preferably with n being 1, which contains at least one heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen.

Particularly preferred are tricyanoborates of formula I which have a divalent organic cation Q²⁺, such as, for example, ethylenediammonium.

Further particularly preferred are tricyanoborates of formula I which have a monovalent organic cation Q⁺ selected from the group consisting of cations of formula

-   (a) (WR²R³R⁴R⁵)⁺, wherein W is a nitrogen or phosphorus, and     -   (i) wherein R² to R⁴ are, independently, C₁₋₂₀ alkyl, and R⁵ is         C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein optionally         R² to R⁵, independently, contain one or more halogens, or     -   (ii) wherein R² and R³ together with W form a 5- to 7-membered         ring and R⁴ and R⁵ are, independently, C₁₋₂₀ alkyl, wherein         optionally R⁴ and R⁵, independently, contain one or more         halogens, or     -   (iii) wherein R² and R³ or R⁴ and R⁵ in each case together with         W form a 5- to 7-membered ring, or -   (b) (XR⁶R⁷R⁸)⁺, wherein X is nitrogen and R⁶ and R⁷ together with X     form a ring in which X formally has one single bond and one double     bond to R⁶ and R⁷, and R⁸ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀     aryl, wherein R⁸ optionally contains one or more halogens, or -   (c) (YR⁹R¹⁰R¹¹)⁺, wherein Y is sulfur and     -   (i) wherein R⁹ and R¹⁰ are, independently, C₁₋₂₀ alkyl and R¹¹         is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein         optionally R⁹ to R¹¹, independently, contain one or more         halogens, or     -   (ii) wherein R⁹ and R¹⁰ together with Y form a 5- to 7-membered         ring and R¹¹ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl,         wherein R¹¹ optionally contains one or more halogens, or -   (d) (ZR¹²R¹³)⁺, wherein Z is oxygen or sulfur and R¹² and R¹³     together with Z form a ring in which Z formally has one single bond     and one double bond to R¹² and R¹³, and     wherein optionally one or more substituents selected from the group     consisting of C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, C₃₋₁₀ cycloalkyl, C₆₋₁₀     aryl, halogen and cyano are bound to each of the rings formed with     the substituents R² to R¹³, wherein optionally the C₁₋₂₀ alkyl, the     C₁₋₂₀ alkoxy, the C₃₋₁₀ cycloalkyl and the C₆₋₁₀ aryl,     independently, contain one or more halogens, and     wherein optionally each of the rings formed with the substituents R²     to R¹³ contains one or two further, substituted or unsubstituted     heteroatoms selected from the group consisting of nitrogen, sulfur     and oxygen and/or be fused to another aromatic or non-aromatic 5- to     7-membered ring. A suitable substituent of the heteroatom is, for     example, C₁₋₈ alkyl.

Here and in the following, the expression “C_(3-n) cycloalkyl” refers to a cycloalkyl group having from 3 to n carbon atoms. “C₃₋₁₀ cycloalkyl” represents, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl.

Here and in the following, the expression “C_(1-n) alkoxy” refers to an unbranched or branched alkoxy group having from 1 to n carbon atoms. “C₁₋₂₀ alkoxy” represents, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, 1,4-dimethylpentyloxy, hexyloxy, heptyloxy, octyloxy, 1,5-dimethyl-hexyloxy, nonyloxy, decyloxy, 4-ethyl-1,5-dimethylhexyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or eicosyloxy.

Here and in the following, the expression “halogen” refers to fluorine, chlorine, bromine or iodine.

Particularly preferred are tricyanoborates of formula I with an organic cation Q⁺ selected from the group consisting of organic ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, imidazolium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,3-dioxolium, pyrylium and thiopyrylium cation.

Preferably, the organic cation Q⁺ is selected from the group consisting of

wherein R and R′ are, independently, C₁₋₂₀ alkyl, preferably C₁₋₁₄ alkyl and more preferably C₁₋₈ alkyl, and m is an integer between 0 and 4. Favorably, the substituents R and R′ have different lengths.

More preferably, the organic cation Q⁺ is selected from the group consisting of

In a further particularly preferred embodiment, the organic cations Q⁺ are imidazolium cations, in particular imidazolium cations of the general formula

wherein R and R′ are, independently, C₁₋₂₀ alkyl, preferably C₁₋₁₄ alkyl. In a most preferred embodiment, R is methyl and R′ is ethyl.

In particular, the compound 1-ethyl-3-methylimidazolium tricyanomethoxyborate is claimed.

Tricyanoborates with an organic cation are usually liquid at temperatures below 100° C., in particular at room temperature, and are therefore referred to as ionic liquids. Owing to their property as ionic liquids, they are highly suitable as solvents for many organic and inorganic substances.

Therefore, claimed is the use of the tricyanoborate of formula I, wherein R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl, X is oxygen or sulfur and Cat^(n+) is an organic cation Q^(n+) with n being 1 or 2, preferably with n being 1, optionally in a mixture with one or more other ionic liquids, water or organic solvents, as polar aprotic solvent.

Ionic liquids have many fields of use: They extend from the use as solvent in inorganic and organic synthesis through the use as electrolyte to release agents and/or additives for lubricants and hydraulic fluids. The spectrum of specific requirements which the ionic liquids have to meet in order to be suitable for a specific application is therefore correspondingly broad. The ionic liquids of the invention are characterized by, in particular, a non-coordinating anion. In addition, they are halogen-free, which makes inexpensive and environmentally friendly disposal possible, for example by incineration, and, owing to the low corrosivity towards metals, simplifies their use and storage.

The properties of the ionic liquids according to the invention can be varied by choice of suitable organic cations and suitable substituents —X—R¹ of the borate anion. Thus, for example, the melting point, the thermal and electrochemical stability, the viscosity, the polarity and the solubility in water or in organic solvents can be strongly influenced by variation of the substituents —X—R¹ of the borate anion and also by variation of the organic cation and its substituents.

Further, the present invention relates to a process for preparing the inorganic tricyano-borates of formula I, wherein R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl, X is oxygen or sulfur and Cat^(n+) is an inorganic cation M^(n+) with n being 1 or 2, preferably selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺, characterized in that

B(XR¹)₃ is reacted with a cyanotri-C₁₋₆-alkylsilane, in particular with cyanotrimethyl-silane (TMSCN), in the presence of M^(n+)(CN⁻)_(n), wherein

R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl,

X is oxygen or sulfur, and

M^(n+) is an inorganic cation with n being 1 or 2, preferably selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.

Preferably, B(XR¹)₃ and M^(n+)(CN⁻)_(n) are applied in a molar ratio of from 0.8:1.0 to 1.2:1.0, in particular in a molar ratio of from 0.9:1.0 to 1.1:1.0. The cyanotri-C₁₋₆-alkylsilane is preferably used in an excess based on B(XR¹)₃, for example in a molar ratio of from 1.5:1 to 10:1, in particular in a molar ratio of from 3:1 to 5:1. The process for preparing the inorganic tricyanoborates is preferably carried out at a temperature of from 0° C. to 250° C., in particular at a temperature of from 50° C. to 100° C. Preferably, the process for preparing the inorganic tricyanoborates is carried out at a temperature which is above the boiling point of the alkoxytri-C₁₋₆-alkylsilane formed as side product.

The present invention also relates to a process for preparing the organic tricyano-borates of formula I, wherein R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl, X is oxygen or sulfur and Cat^(n+) is an organic cation Q^(n+) with n being 1 or 2, preferably n being 1, characterized in that

the inorganic tricyanoborates of formula I, wherein R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl, X is oxygen or sulfur and Cat^(n+) is an inorganic cation M^(n+) with n being 1 or 2, preferably selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺, are reacted with a salt of formula (Q^(n+))_(p)(Y^(p−))_(n), wherein Q^(n+) is an organic cation, in particular an organic cation containing at least one heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen, n is 1 or 2, Y^(p−) is an anion selected from the group consisting of halides, pseudohalides, sulfate and organic acid anions and p is 1 or 2.

In a preferred embodiment, the inorganic tricyanoborates used are prepared precedent according to the process for their preparation as claimed above.

The halide as anion Y⁻ of the salt of the formula (Q^(n+))(Y⁻)_(n) can be selected from the group consisting of fluoride, chloride, bromide and iodide. Particularly preferred is chloride.

As pseudohalide anions Y⁻ in the salt (Q^(n+))(Y⁻)_(n), anions which consist of at least two electronegative atoms and which are chemically similar to the halogens can be used. Preferably, the pseudohalide anion is selected from the group consisting of CN⁻, OCN⁻, SCN⁻ and N₃ ⁻. More preferably, the pseudohalide anion is CN⁻.

Suitable examples for organic acid anions are anions of monobasic and dibasic non-aromatic and aromatic acids, such as acetate, oleate, fumarate, maleate, pyruvate, oxalate and benzoate. Particularly preferred are acetate and pyruvate anions.

When n and p are 1, and when n and p are 2, the inorganic tricyanoborate as defined above and the salt of the formula QY are preferably used in a molar ratio of from 0.8:1.0 to 1.2:1.0, in particular in a molar ratio of from 0.9:1.0 to 1.1:1.0.

The reaction is preferably carried out in a solvent or solvent mixture, for example in a two-phase solvent mixture comprising water and at least one organic solvent, for example in a mixture of water and methylene chloride. As an alternative, the reaction can also be carried out in the absence of a solvent or in an organic solvent in which the inorganic salt formed as side product is sparingly soluble or insoluble. As a further alternative, it is also possible to carry out the reaction in an aqueous solution using a previously loaded ion exchanger.

The process for preparing the organic tricyanoborates is preferably carried out at a temperature of from 10° C. to 250° C., in particular at a temperature in the range from room temperature to 100° C.

EXAMPLES

Abbreviations:

TMSCN=cyanotrimethylsilane

TMSOMe=methoxytrimethylsilane

EA=elemental analysis

CP-OES=optical emission spectrometry with inductively coupled plasma

br=broad

Example 1 Synthesis of potassium tricyanomethoxyborate K[B(CN)₃(OCH₃)]

B(OCH₃)₃ (20.0 g, 0.19 mol) and KCN (12.5 g, 0.19 mol) were dissolved in TMSCN (66.8 g, 0.67 mol) and heated at a reflux temperature of 70° C. under protective gas for 18 hours. After cooling, all volatile components (unreacted TMSCN, formed TMSOMe) were distilled off to give powdery K[B(CN)₃(OCH₃)] in a yield of 27.8 g (92%).

¹H-NMR (400 MHz, CD₃CN, TMS): δ [ppm]=3.22 (q, J_(H/B)=3.5 Hz, 3H).

¹³C-NMR (125 MHz, CD₃CN, TMS): δ [ppm]=53.26 (s); 128.7 (q (80%)+septet (20%), q: J=69.9 Hz, septet: J=23.0 Hz).

¹¹B-NMR (160.3 MHz, CD₃CN, BF₃.Et₂O external): δ [ppm]=−18.5 (s).

IR (Nujol): ν [cm⁻¹]=2228, 2163, 1201, 1221 br, 965, 926, 866.

Melting point: >240° C. (decomposition).

Analysis:

Element C H N B K Method EA EA EA CP-OES CP-OES % expected 30.22 1.90 26.43 6.80 24.29 % found 30.50 2.20 25.70 6.90 21.13

Example 2 Synthesis of 1-ethyl-3-methylimidazolium tricyanomethoxyborate (ionic liquid)

An aqueous solution of 1-ethyl-3-methylimidazolium chloride (5.0 g, 34 mmol), K[B(CN)₃(OCH₃)] (5.4 g, 34 mmol) and water (25.1 g) were mixed with methylene chloride (67 g) and stirred at room temperature for 1 hour. After separation of the aqueous and the organic phase, the organic phase was washed with 10 ml of water and evaporated on a rotary evaporator yielding 5.81 g (74%) of 1-ethyl-3-methyl-imidazolium tricyanomethoxyborate as a colorless, low-viscosity liquid which did not solidify even at a temperature of −10° C.

¹H-NMR (400 MHz, CD₃CN, TMS): δ [ppm]=1.62 (br t, J=7.0 Hz, 3H), 3.33 (q, J_(H/B)=3.5 Hz, 3H), 4.01 (s, 3H), 4.30 (br q, J=7.0 Hz, 2H), 7.36 (s, 1H), 7.39 (s, 1H), 8.67 (s, 1H).

¹³C-NMR (125 MHz, CD₃CN, TMS): δ [ppm]=15.1 (s), 36.8 (br), 45.7 (s), 53.3 (s), 122.3 (br), 124.0 (br), 128.3 (q (80%)+septet (20%), q: J=69.9 Hz, septet: J=23.0 Hz).

Melting point: Below 0° C.

Example 3 Synthesis of 1-ethyl-3-methylimidazolium tricyanomethoxyborate (ionic liquid)

A solution of 1-ethyl-3-methylimidazolium chloride (5.0 g, 34 mmol) in water (25 ml) and K[B(CN)₃(OCH₃)] (5.4 g, 34 mmol) were mixed with methylene chloride (67 g) and stirred at room temperature for 3 hours. After separation of the aqueous and the organic phase, the latter was washed with 10 ml of water, dried over potassium carbonate and finally evaporated on a rotary evaporator yielding 3.78 g (48%) of 1-ethyl-3-methylimidazolium tricyanomethoxyborate as a low-viscosity liquid.

¹H-NMR (400 MHz, CD₃CN, TMS): δ [ppm]=1.62 (br t, J=7.0 Hz, 3H), 3.33 (q, J_(H/B)=3.5 Hz, 3H), 4.01 (s, 3H), 4.30 (br q, J=7.0 Hz, 2H), 7.36 (s, 1H), 7.39 (s, 1H), 8.67 (s, 1H).

¹³C-NMR (125 MHz, CD₃CN, TMS): δ [ppm]=15.1 (q), 36.8 (br), 45.7 (br), 53.3 (q), 122.3 (br), 124.0 (br), 128.3 (q (80%)+septet (20%), q: J=69.9 Hz, septet: J=23.2 Hz), 135.7 (d).

Melting point: Below 0° C.

Example 4 Synthesis of N-n-butyl-2-picolinium tricyanomethoxyborate (ionic liquid)

A solution of N-n-butyl-2-picolinium chloride (5.0 g, 27 mmol) in water (20 ml) and K[B(CN)₃(OCH₃)] (4.3 g, 27 mmol) were mixed with methylene chloride (53 g) and stirred at room temperature for 5 hours. After separation of the aqueous and the organic phase, the latter was washed with 10 ml of water, dried over potassium carbonate and finally evaporated on a rotary evaporator yielding 4.0 g (55%) of N-n-butyl-2-picolinium tricyanomethoxyborate as a low-viscosity liquid.

¹H-NMR (500 MHz, CD₃CN, TMS): δ [ppm]=0.92 (t, J=7.3 Hz, 3H), 1.35-1.43 (m, 2H), 1.79-1.83 (m, 2H), 2.74 (s, 3H), 3.15 (q, J_(H/B)=3.9 Hz, 3H), 4.39 (br t, J=8 Hz, 2H), 7.76-7.82 (m, 2H), 8.26-8.30 (m, 1H), 8.52-8.54 (m, 1H).

¹³C-NMR (125 MHz, CD₃CN, TMS): δ [ppm]=12.9 (q), 19.4 (q), 19.7 (t), 31.7 (t), 52.5 (q), 58.0 (t), 126.0 (d), 128.0 (q (80%)+septet (20%), q: J=69.9 Hz, septet: J=20.7 Hz), 130.5 (d), 145.1 (d), 145.3 (d), 155.61 (s).

Melting point: Below 0° C.

Example 5 Synthesis of Tetraethylammonium Tricyanomethoxyborate (Ionic Liquid)

A solution of tetraethylammonium chloride (5.0 g, 30 mmol) in water (22 ml) and K[B(CN)₃(OCH₃)] (4.8 g, 30 mmol) were mixed with methylene chloride (59 g) and stirred at room temperature for 5 hours. After separation of the aqueous and the organic phase, the latter was washed with 10 ml of water, dried over potassium carbonate and finally evaporated on a rotary evaporator yielding 4.0 g (53%) of tetraethylammonium tricyanomethoxyborate as a low-viscosity liquid.

¹H-NMR (500 MHz, CD₃CN, TMS): δ [ppm]=1.16 (tt, J=7.3, J_(H/N)=1.9 Hz, 12H), 3.12 (q, J=7.3 Hz, 8H), 3.16 (J_(H/B)=3.4 Hz, 3H).

¹³C-NMR (125 MHz, CD₃CN, TMS): δ [ppm]=6.8 (q), 52.3 (dt, J_(C/N)=3.2 Hz), 54.5 (q), 128.0 (q (80%)+septet (20%), q: J=70 Hz, septet: J=23.5 Hz).

Melting range (DSC): Between 1 and 26° C.

Example 6 Synthesis of Tetrabutylphosphonium Tricyanomethoxyborate (Ionic Liquid)

A solution of tetrabutylphosphonium methanesulfonate (5.0 g, 14 mmol) in water (10.4 ml) and K[B(CN)₃(OCH₃)] (2.2 g, 14 mmol) were mixed with methylene chloride (27.6 g) and stirred at room temperature for 5 hours. After separation of the aqueous and the organic phase, the latter was washed with 10 ml of water, dried over potassium carbonate and finally evaporated on a rotary evaporator yielding 3.4 g (64%) of tetrabutylphosphonium tricyanomethoxyborate as a low-viscosity liquid.

¹H-NMR (500 MHz, CD₃CN, TMS): δ [ppm]=0.95 (t, J=7.3 Hz, 12H), 1.44-1.53 (m, 16H), 2.04-2.10 (m, 8H), 3.21 (J_(H/B)=3.4 Hz, 3H).

¹³C-NMR (125 MHz, CD₃CN, TMS): δ [ppm]=13.76 (br q), 19.2 (td, J_(P/C)=48.3 Hz), 24.1 (td, J_(P/C)=4.6 Hz), 24.7 (td, J_(P/C)=15.6), 53.4 (q), 128.0 (q+m, q: J=70 Hz).

Melting point: Below 0° C. 

1. A tricyanoborate of formula

wherein R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl, X is oxygen or sulfur, and Cat^(n+) is a cation with n being 1 or 2, which is selected from the group consisting of an inorganic cation and an organic cation.
 2. The tricyanoborate according to claim 1, wherein X is oxygen.
 3. The tricyanoborate according to claim 1, wherein R¹ is methyl, ethyl or propyl.
 4. The tricyanoborate according to claim 3, wherein R¹ is methyl.
 5. The tricyanoborate according to claim 1, wherein Cat^(n+) is an inorganic cation selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.
 6. The tricyanoborate according to claim 1, wherein Cat^(n+) is an organic cation containing at least one heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen.
 7. The tricyanoborate according to claim 6, wherein the organic cation is selected from the group consisting of cations of formula (a) (WR²R³R⁴R⁵)⁺, wherein W is nitrogen or phosphorus, and (i) wherein R² to R⁴ are, independently, C₁₋₂₀ alkyl, and R⁵ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein optionally R² to R⁵, independently, contain one or more halogens, or (ii) wherein R² and R³ together with W form a 5- to 7-membered ring and R⁴ and R⁵ are, independently, C₁₋₂₀ alkyl, wherein optionally R⁴ and R⁵, independently, contain one or more halogens, or (iii) wherein R² and R³ or R⁴ and R⁵ in each case together with W form a 5- to 7-membered ring, or (b) (XR⁶R⁷R⁸)⁺, wherein X is nitrogen and R⁶ and R⁷ together with X form a ring in which X formally has one single bond and one double bond to R⁶ and R⁷, and R⁸ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein R⁸ optionally contains one or more halogens, or (c) (YR⁹R¹⁰R¹¹)⁺, wherein Y is sulfur and (i) wherein R⁹ and R¹⁰ are, independently, C₁₋₂₀ alkyl and R¹¹ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein optionally R⁹ to R¹¹, independently, contain one or more halogens, or (ii) wherein R⁹ and R¹⁰ together with Y form a 5- to 7-membered ring and R¹¹ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein R¹¹ optionally contains one or more halogens, or (d) (ZR¹²R¹³)⁺, wherein Z is oxygen or sulfur and R¹² and R¹³ together with Z form a ring in which Z formally has one single bond and one double bond to R¹² and R¹³, and wherein optionally one or more substituents selected from the group consisting of C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, C₃₋₁₀ cycloalkyl, C₆₋₁₀ aryl, halogen and cyano are bound to each of the rings formed with the substituents R² to R¹³, wherein optionally the C₁₋₂₀ alkyl, the C₁₋₂₀ alkoxy, the C₃₋₁₀ cycloalkyl and the C₆₋₁₀ aryl, independently, contain one or more halogens, and wherein optionally each of the rings formed with the substituents R² to R¹³ contains one or two further, substituted or unsubstituted heteroatoms selected from the group consisting of nitrogen, sulfur and oxygen and/or be fused to another aromatic or non-aromatic 5- to 7-membered ring.
 8. The tricyanoborate according to claim 6, wherein the organic cation is selected from the group consisting of organic ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, imidazolium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,3-dioxolium, pyrylium and thiopyrylium cation.
 9. The tricyanoborate according to claim 6, wherein the organic cation is selected from the group consisting of

wherein R and R′ are, independently, C₁₋₂₀ alkyl, and m is an integer from 0 to
 4. 10. The tricyanoborate according to claim 9, wherein the organic cation is of formula

wherein R and R′ are, independently, C₁₋₂₀ alkyl.
 11. The tricyanoborate according to claim 10, wherein R is methyl and R′ is ethyl.
 12. A process for preparing the tricyanoborate as defined in claim 5, comprising reacting characterized in that B(XR¹)₃ with a cyanotri-C₁₋₆-alkylsilane in the presence of M^(n+)(CN⁻)_(n), wherein R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl, X is oxygen or sulfur, and M^(n+) is an inorganic cation with n being 1 or 2, selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.
 13. A process for preparing the tricyanoborate as defined in claim 6 comprising reacting a tricyanoborate of formula (I)

with a salt of formula (Q^(n+))_(p) (Y^(p−))_(n), wherein R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl, X is oxygen or sulfur, Cat^(n+) is an inorganic cation selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺, Q^(n+) is an organic cation containing at least one heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen, n is 1 or 2, Y^(p−) is an anion selected from the group consisting of halides, pseudohalides, sulfate and organic acid anions, and p is 1 or
 2. 14. The process according to claim 13, wherein the tricyanoborate that is reacted with a salt of formula (Q^(n+))_(p)(Y^(p−))_(n) is prepared precedent according to the process of reacting B(XR¹)₃ with a cyanotri-C₁₋₆-alkylsilane in the presence of M^(n+)(CN⁻)_(n), wherein R¹ is C₁₋₆ alkyl, C₂₋₆ alkenyl, C₆₋₁₀ aryl or benzyl, X is oxygen or sulfur, and M^(n+) is an inorganic cation with n being 1 or 2, selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.
 15. The tricyanoborate according to claim 2, wherein R¹ is methyl, ethyl or propyl.
 16. The tricyanoborate according to claim 15, wherein R¹ is methyl.
 17. The tricyanoborate according to claim 2, wherein Cat^(n+) is an inorganic cation selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.
 18. The tricyanoborate according to claim 3, wherein Cat^(n+) is an inorganic cation selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.
 19. The tricyanoborate according to claim 4, wherein Cat^(n+) is an inorganic cation selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, NH₄ ⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺.
 20. The tricyanoborate according to claim 2, wherein Cat^(n+) is an organic cation containing at least one heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen.
 21. The tricyanoborate according to claim 3, wherein Cat^(n+) is an organic cation containing at least one heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen.
 22. The tricyanoborate according to claim 4, wherein Cat^(n+) is an organic cation containing at least one heteroatom selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen.
 23. The tricyanoborate according to claim 7, wherein X is oxygen.
 24. The tricyanoborate according to claim 7, wherein R¹ is methyl, ethyl or propyl.
 25. The tricyanoborate according to claim 7, wherein R¹ is methyl.
 26. The tricyanoborate according to claim 7, wherein the organic cation is selected from the group consisting of organic ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, imidazolium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,3-dioxolium, pyrylium and thiopyrylium cation.
 27. The tricyanoborate according to claim 7, wherein the organic cation is selected from the group consisting of

wherein R and R′ are, independently, C1-20 alkyl, and m is an integer from 0 to
 4. 28. The tricyanoborate according to claim 8, wherein the organic cation is selected from the group consisting of

wherein R and R′ are, independently, C₁₋₂₀ alkyl, and m is an integer from 0 to
 4. 29. The process according to claim 13, wherein the organic cation Q^(n+) is selected from the group consisting of cations of formula (a) (WR²R³R⁴R⁵)⁺, wherein W is nitrogen or phosphorus, and (i) wherein R² to R⁴ are, independently, C₁₋₂₀ alkyl, and R⁵ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein optionally R² to R⁵, independently, contain one or more halogens, or (ii) wherein R² and R³ together with W form a 5- to 7-membered ring and R⁴ and R⁵ are, independently, C₁₋₂₀ alkyl, wherein optionally R⁴ and R⁵, independently, contain one or more halogens, or (iii) wherein R² and R³ or R⁴ and R⁵ in each case together with W form a 5- to 7-membered ring, or (b) (XR⁶R⁷R⁸)⁺, wherein X is nitrogen and R⁶ and R⁷ together with X form a ring in which X formally has one single bond and one double bond to R⁶ and R⁷, and R⁸ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein R⁸ optionally contains one or more halogens, or (c) (YR⁹R¹⁰R¹¹), wherein Y is sulfur and (i) wherein R⁹ and R¹⁰ are, independently, C₁₋₂₀ alkyl and R¹¹ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein optionally R⁹ to R¹¹, independently, contain one or more halogens, or (ii) wherein R⁹ and R¹⁰ together with Y form a 5- to 7-membered ring and R¹¹ is C₁₋₂₀ alkyl, C₃₋₁₀ cycloalkyl or C₆₋₁₀ aryl, wherein R¹¹ optionally contains one or more halogens, or (d) (ZR¹²R¹³)⁺, wherein Z is oxygen or sulfur and R¹² and R¹³ together with Z form a ring in which Z formally has one single bond and one double bond to R¹² and R¹³, and wherein optionally one or more substituents selected from the group consisting of C₁₋₂₀ alkyl, C₁₋₂₀ alkoxy, C₃₋₁₀ cycloalkyl, C₆₋₁₀ aryl, halogen and cyano are bound to each of the rings formed with the substituents R² to R¹³, wherein optionally the C₁₋₂₀ alkyl, the C₁₋₂₀ alkoxy, the C₃₋₁₀ cycloalkyl and the C₆₋₁₀ aryl, independently, contain one or more halogens, and wherein optionally each of the rings formed with the substituents R² to R¹³ contains one or two further, substituted or unsubstituted heteroatoms selected from the group consisting of nitrogen, sulfur and oxygen and/or be fused to another aromatic or non-aromatic 5- to 7-membered ring.
 30. The process according to claim 13, wherein the organic cation Q^(n+) is selected from the group consisting of organic ammonium, phosphonium, sulfonium, pyrrolidinium, pyrrolinium, pyrrolium, pyrazolium, imidazolium, triazolium, oxazolium, thiazolium, piperidinium, piperazinium, morpholinium, pyridinium, pyridazinium, pyrimidinium, pyrazinium, 1,3-dioxolium, pyrylium and thiopyrylium cation.
 31. The process according to claim 13, wherein the organic cation Q^(n+) is selected from the group consisting of

wherein R and R′ are, independently, C₁₋₂₀ alkyl, and m is an integer from 0 to
 4. 32. The process according to claim 31, wherein the organic cation Q^(n+) is of formula

wherein R and R′ are, independently, C₁₋₂₀ alkyl.
 33. The process according to claim 32, wherein R is methyl and R′ is ethyl. 